Classifications

• • A—HUMAN NECESSITIES
  • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
  • A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
  • A47J36/00—Parts, details or accessories of cooking-vessels
  • A47J36/02—Selection of specific materials, e.g. heavy bottoms with copper inlay or with insulating inlay
  • A47J36/025—Vessels with non-stick features, e.g. coatings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/62—Plasma-deposition of organic layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
  • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
  • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/52—Two layers

Definitions

• the present invention generally relates to cookware having a nonstick coating, and more particularly to cookware having a fluorocarbon resin release coating having improved adhesion properties to the carrier.
• the present invention also relates to a method of manufacturing such a culinary article.
• a sintered fluorocarbon resin (eg, PTFE) coating is used as the release coating on the inside of a culinary article.
• PTFE sintered fluorocarbon resin
• Such coatings are known not only for their non-stick properties, but also for their resistance to chemical or thermal attack.
• a primer comprising a bonding binder such as PAI
• chemical surface treatments for example of the chemical stripping type
• mechanical for example by brushing or sandblasting
• a surface chemical treatment of the stripping type involves the use of polluting chemical baths and a mechanical surface treatment of the brushing or sandblasting type deforms (slightly) the surface, which imposes an additional conformation operation.
• the medium of sanding or the brushes must be regenerated or put in discharge at the end of life which generates pollutions.
• the Applicant has developed a plasma surface treatment that allows the formation of an interface layer between the support and the release coating, this interface layer improving the latter anchor on the support and thus allowing the coating to ensure a long-term function without risk of delamination.
• the subject of the present invention is an article comprising a support having an at least partially metallic contact surface and which is covered by a non-stick coating comprising at least one layer comprising at least one fluorocarbon resin alone or in admixture with a binder. thermostable bond and resistant to at least 200 ° C, the fluorocarbon resin and, where appropriate, the thermostable bonding binder forming a sintered network,
• said contact surface (comprises an interface layer consisting of a polymer layer formed by plasma polymerization from a precursor selected from unsaturated carboxylic acids, their salts, their esters, the vinyl esters of acids saturated carboxylic acids, unsaturated dicarboxylic acids, their salts, esters, hemiesters, anhydrides, and unsaturated epoxides.
• the contact surface is entirely metallic
• a metal support partially covered with a hard base in this case, the contact surface is partially metallic, the complement being constituted by the base hard
• the hard base being preferably enamel or ceramic.
• the metal part of the support is preferably aluminum or aluminum alloy, cast aluminum (or foundry aluminum alloy), or stainless steel.
• cooking utensils As non-limiting examples of cooking utensils according to the present invention, mention may in particular be made of culinary articles such as pots and pans, oks and sauté-pans, facts-wholes and pots, crepe makers, grills. , molds and plates for baking, barbecue plates and grills, bowls for preparation.
• culinary articles such as pots and pans, oks and sauté-pans, facts-wholes and pots, crepe makers, grills. , molds and plates for baking, barbecue plates and grills, bowls for preparation.
• an unsaturated carboxylic acid mention may be made of methacrylic acid.
• an unsaturated dicarboxylic acid mention may be made of maleic anhydride.
• vinyl or allyl esters of saturated carboxylic acids mention may be made of vinyl acetate.
• unsaturated epoxides mention may be made of glycidyl methacrylate.
• the interface layer formed by plasma polymerization can thus advantageously be a polymeric layer consisting essentially of glycidyl polymethacrylate or poly (maleic anhydride).
• the non-stick coating may comprise a layer of primer and at least one topcoat, the said primer layer comprising, in addition to the sintered network fluorocarbon resin, at least one bonding binder.
• the contact surface may also be advantageous for the contact surface to be a surface previously chemically or mechanically treated.
• Such a treatment also makes it possible to modify the surface states and to reach, in particular, surface tensions of the order of 72 ⁇ m / m on aluminum supports, which improves the wettability of the substrate.
• this treatment creates a nanometric oxidation layer which is favorable to adhesion if the coating is applied quickly after the plasma treatment (of the order of at most 60 seconds for apply the non-stick coating to the support treated by plasma).
• the plasma treatment of the order of at most 60 seconds for apply the non-stick coating to the support treated by plasma.
• the fluorocarbon resin used in the non-stick coating of the article according to the invention may advantageously be chosen from polytetrafluoroethylene (PTFE), the copolymer of tetrafluoroethylene and perfluoropropylvinylether (PFA), the copolymer of tetrafluoroethylene and hexafluoropropylene (FEP), and mixtures thereof (in particular a mixture of PTFE and PFA).
• PTFE polytetrafluoroethylene
• PFA perfluoropropylvinylether
• FEP hexafluoropropylene
• mixtures thereof in particular a mixture of PTFE and PFA.
• the bonding binder used in the non-stick coating of the article according to the invention may advantageously be chosen from polyamide imides (PAI), polyether imides (PEI), polyamides (PI), polyetherketones (PEK), polyetheretherketones (PEEK), polyethersulfones (PES) and polyphenylene sulfides (PPS).
• PAI polyamide imides
• PEI polyether imides
• PI polyamides
• PEK polyetherketones
• PEEK polyetheretherketones
• PES polyethersulfones
• PPS polyphenylene sulfides
• the present invention also relates to a method of manufacturing an article according to the invention, comprising the following steps:
• compositions based on at least one fluorocarbon resin in particulate form said fluorocarbon resin being alone or in admixture with a thermostable bonding binder and resistant to at least 200 ° C .;
• said method being characterized in that it further comprises, before the application of the fluorocarbon resin composition on the surface of the support (contact surface), a plasma polymerization step to form, on said contact surface, a polymer layer from a precursor selected from unsaturated carboxylic acids, their salts, their esters, the vinyl esters of saturated carboxylic acids, the unsaturated dicarboxylic acids, their salts, their esters, their hemiesters, their anhydrides, and unsaturated epoxides.
• a plasma polymerization step to form, on said contact surface, a polymer layer from a precursor selected from unsaturated carboxylic acids, their salts, their esters, the vinyl esters of saturated carboxylic acids, the unsaturated dicarboxylic acids, their salts, their esters, their hemiesters, their anhydrides, and unsaturated epoxides.
• the fluorocarbon resin and the thermostable bonding binder are as defined above.
• an unsaturated carboxylic acid mention may be made of methacrylic acid.
• an unsaturated dicarboxylic acid mention may be made of maleic anhydride.
• vinyl or allyl esters of saturated carboxylic acids mention may be made of vinyl acetate.
• maleic anhydride or glycidyl methacrylate are preferably used as precursors.
• the formation of the non-stick coating may comprise:
• primer composition comprising at least one fluorocarbon resin in particulate form and at least one heat-stable bonding binder; and resistant to at least 200 ° C;
• topcoat composition to form a topcoat, the topcoat comprising at least one fluorocarbon resin in particulate form.
• the contact surface is chemically treated (for example defatted or satin) or mechanically (especially brushed).
• it is possible to form a nonstick coating by applying, directly to the previously treated contact surface, at least one finishing composition substantially free of bonding binder, to form at least one topcoat.
• FIG. 1 represents a diagrammatic sectional view of an example of a culinary article according to the invention according to the prior art (non-plasma treated support and primer);
• FIG. 2 represents a schematic sectional view of a culinary article according to the invention (support treated by plasma polymerization with a primer);
• FIGS. 1 and 2 are identical elements shown in FIGS. 1 and 2 are identified by identical reference numerals.
• FIGS. 1 and 2 show, as an example of an article according to the invention, a pan 1 comprising a support metal 2 being in the form of hollow cap and a gripping handle 5.
• the support 2 comprises an inner face 21 (contact surface) which is the side facing the side of the food that can be received in the pan 1, and a outer face 22 which is intended to be disposed towards an external heat source.
• the inner face 21 is coated with a non-stick coating 3, which comprises successively from the support 2 a primer coat 30 and two topcoats 31, 32.
• the primer layers 30, finish 31 and decor 32 are based on PTFE.
• the support 2 of the pan shown in FIG. 1 has not been plasma treated in accordance with the present invention, whereas that of the pan shown in FIG. 2 has been treated by plasma polymerization, leading to the formation of a polymer layer 210 on the contact surface 21 of the support.
• LUDOX AM30 (colloidal silica in 30% water): 21.5 g PTFE (60% PTFE dispersion) 78 g
• PAI resin (29% dry in CIP): 58.9 g
• LUDOX AM30 (colloidal silica in water 30%): 19.3 g
• ⁇ deposition reactor consisting of a cylindrical stainless steel enclosure equipped with devices for measuring and introducing materials and precursors, as well as evacuation devices (10 ⁇ 3 mmHg) o process comprising:
• a grid test is performed according to ISO 2409 followed by immersion of the article for 9 hours (3 cycles of 3 hours in boiling water). Then, it is observed whether or not the non-stick coating has a detachment.
• the quotation is as follows:
• the adhesion of the non-stick coating on the support is considered industrially acceptable if one has a value equal to or greater than 95 this level of adhesion is then suitable for any type of cookware regardless of its level of mechanical stress.
• the platelet assembly was coated with a non-stick coating 3, whether or not comprising a primer composition (CP1 or CP2) and a finishing composition, after having been previously or not subjected to a plasma treatment in accordance with the method according to the invention.
• a non-stick coating 3 whether or not comprising a primer composition (CP1 or CP2) and a finishing composition, after having been previously or not subjected to a plasma treatment in accordance with the method according to the invention.
• the plasma treatment according to the method of the invention makes it possible to dispense with the presence of a primer layer.
• the plasma treatment makes it possible to overcome the presence of a PAI type binder in the primer layer (for any type of precursor), or even a primer layer (with in particular a precursor such as glycidyl methacrylate).

Landscapes

• Engineering & Computer Science (AREA)
• Food Science & Technology (AREA)
• Physics & Mathematics (AREA)
• Plasma & Fusion (AREA)
• Laminated Bodies (AREA)
• Paints Or Removers (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Frying-Pans Or Fryers (AREA)
• Cookers (AREA)
• Adhesives Or Adhesive Processes (AREA)

Applications Claiming Priority (2)

Publications (2)

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• 2011
  • 2011-08-26 FR FR1157580A patent/FR2979215B1/fr not_active Expired - Fee Related
• 2012
  • 2012-08-27 KR KR1020147007981A patent/KR102023212B1/ko active IP Right Grant
  • 2012-08-27 EP EP12756794.9A patent/EP2747902B1/de active Active
  • 2012-08-27 ES ES12756794.9T patent/ES2558480T3/es active Active
  • 2012-08-27 CN CN201280041582.7A patent/CN103958076B/zh active Active
  • 2012-08-27 WO PCT/FR2012/051939 patent/WO2013030502A1/fr active Application Filing
  • 2012-08-27 US US14/240,957 patent/US20140305948A1/en not_active Abandoned

Non-Patent Citations (1)

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